JP5770094B2 - 新規オルガノポリシロキサン共重合体 - Google Patents
新規オルガノポリシロキサン共重合体 Download PDFInfo
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- JP5770094B2 JP5770094B2 JP2011537337A JP2011537337A JP5770094B2 JP 5770094 B2 JP5770094 B2 JP 5770094B2 JP 2011537337 A JP2011537337 A JP 2011537337A JP 2011537337 A JP2011537337 A JP 2011537337A JP 5770094 B2 JP5770094 B2 JP 5770094B2
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- KUPGJMJHAFGISS-UHFFFAOYSA-L zinc;hexadecyl phosphate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCOP([O-])([O-])=O KUPGJMJHAFGISS-UHFFFAOYSA-L 0.000 description 1
- OJYLAHXKWMRDGS-UHFFFAOYSA-N zingerone Chemical compound COC1=CC(CCC(C)=O)=CC=C1O OJYLAHXKWMRDGS-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
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Description
一般式(1):
{式中、R1は独立に炭素原子数1〜10のアルキル基またはアリール基であり、L1はi=1のときの下記一般式(2)で示されるシリルアルキル基であり、Qは親水性セグメントである。nは0〜10の範囲の数である。
一般式(2):
(式中、R2は炭素原子数1〜6のアルキル基またはフェニル基であり、Zは二価の有機基である。iはLiで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がcのとき1〜cの整数であり、階層数cは1〜10の整数であり、Li+1はiがc未満のときは該シリルアルキル基であり、i=cのときはメチル基またはフェニル基である。aiは0〜3の範囲の数である。)}
「[1] 下記一般式(1)で示されるオルガノポリシロキサン共重合体。
一般式(1):
{式中、R1は独立に炭素原子数1〜10のアルキル基またはアリール基であり、L1はi=1のときの下記一般式(2)で示されるシリルアルキル基であり、Qは親水性セグメントである。nは0〜10の範囲の数である。
一般式(2):
(式中、R1は前記と同様の基であり、R2は炭素原子数1〜6のアルキル基またはフェニル基であり、Zは二価の有機基である。iはLiで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がcのとき1〜cの整数であり、階層数cは1〜10の整数であり、Li+1はiがc未満のときは該シリルアルキル基であり、i=cのときはメチル基またはフェニル基である。aiは0〜3の範囲の数である。)}
一般式(2−1):
一般式(2−2):
(式中、R1,R2およびZは前記同様の基であり、a1およびa2は各々独立に0〜3の範囲の数である。)
(式中、Wは水素原子または炭素原子数1〜20のアルキル基。)
(式中、Wは前記同様の基)
Qが二価以上の連結基を介してケイ素原子に結合し、上記構造式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が直鎖状に結合してなる親水性セグメントまたは二価以上の連結基を介してケイ素原子に結合し、かつ上記構造式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位を1以上含有してなり、かつ下記構造式(3−5)〜(3−7)で表される基から選択される分岐単位を有する親水性セグメントである、[1]〜[3]のいずれか1項に記載のオルガノポリシロキサン共重合体。
一般式(4−1):
−R3(−O−X1 m−R4)p (4−1)
(式中、R3は(p+1)価の有機基であり、pは1以上の数である。X1は各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位であり、mは1〜100の範囲の数である。R4は水素原子、炭素原子数1〜20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。)
一般式(4−2):
−R3(−O−X2)p (4−2)
{式中、R3は前記同様の基であり、pは前記同様の数である。X2は下記構造式(4−2−1)で表される親水性単位である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
一般式(4−3):
−R3(−O−X3)p (4−3)
{式中、R3は前記同様の基であり、pは前記同様の数である。X3は下記構造式(4−3−1)で表される親水性単位である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
一般式(4−4):
−R3(−O−X4)p (4−4)
{式中、R3は前記同様の基であり、pは前記同様の数である。X4は下記構造式(4−4−1)で表される親水性単位である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
構造式(1−1):
構造式(1−2):
構造式(1−3):
構造式(1−4):
X1は各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位である。
R´3は下記一般式(5−1),(5−1−2),(5−1−3)または(5−2)で示される2価の有機基から選択される基である。
(式中、R6は、各々独立に、置換基を有していてもよい、炭素数2〜22の直鎖状若しくは分岐鎖状のアルキレン基、アルケニレン基又は炭素数6〜22のアリーレン基である。)
R4は水素原子、炭素原子数1〜20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。
R5は下記一般式(5−1)〜(5−7)で示される2価の有機基から選ばれる基である。
(式中、R6は、前記同様の基である。R7は、下記式で示される二価の有機基から選択される基である。
「[8] [1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する界面活性剤。
[8−2] (a−1)[1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する界面活性剤
(b)シリコーンオイル、非極性有機化合物または低極性有機化合物から選択される油剤
および 水 を含有するエマルジョン組成物。」により達成される。
「[9] [1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する粉体処理剤。
[9−1] (a−2)[1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する粉体処理剤および(d)粉体又は着色剤を含有してなる粉体組成物。
[9−2] (d)粉体又は着色剤 100質量部に対して、(a−2)[1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する粉体処理剤 1.0〜30質量部を使用して前記の(d)成分を表面処理してなることを特徴とする、[9−1]に記載の粉体組成物。
[9−3] 前記の(d)成分が、平均粒子径が1nm〜20μmの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体よりなる群より選ばれる1種又は2種類以上である[9−1]または[9−2]に記載の粉体組成物。
[9−4] 前記の(d)成分が、その一部または全部が撥水化処理された粉体もしくは着色剤であることを特徴とする[9−1]〜[9−3]のいずれか1項に記載の粉体組成物。
[9−5] (a−2)[1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する粉体処理剤、(d)粉体または着色剤および(c)シリコーンオイル、非極性有機化合物または低極性有機化合物から選択される油剤 を含有してなる油中粉体分散物。」により達成される。
「[10] [1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する外用剤組成物。
[11] 化粧料または医薬である[10]に記載の外用剤組成物。
[12] 以下の構成成分を含有する、[11]に記載の化粧料。
(a)[1]〜[7]のいずれか1項に記載のオルガノポリシロキサン共重合体 0.1〜99.9重量%
(b)シリコーンオイル、非極性有機化合物または低極性有機化合物 99.9〜0.1重量%
[13] (b)成分がシリコーンオイルであり、かつ25℃における粘度が0.65〜100,000mm2/sの疎水性シリコーンオイルである[12]に記載の化粧料。
[14] (b)成分が非極性有機化合物または低極性有機化合物であり、該(b)成分が5〜100℃で液状である[12]に記載の化粧料。
[15] シリコーンオイルの一部又は全部が下記一般式(6)で示される直鎖状オルガノポリシロキサン、一般式(7)で示される環状オルガノポリシロキサンまたは一般式(8)で示される分岐状オルガノポリシロキサンの何れかである[12]または[13]に記載の化粧料。
一般式(6):
一般式(7):
一般式(8):
R4−gSi(OSiMe3)g (8)
(上記の一般式(6)〜(8)において、Meはメチル基であり、Rは水素原子、水酸基又は炭素原子数2〜30の一価の非置換又はフッ素置換アルキル基、アリール基、アミノ置換アルキル基、アルコキシ基及び(CH3)3SiO{(CH3)2SiO}hSi(CH3)2CH2CH2−で示される基から選択される基である。
aは独立に0〜3の範囲の整数である。bは0から1000の範囲の整数であり、dは0から1000の範囲の整数であり、(b+d)は1から2000の範囲の整数である。e及びfは0〜8の整数であり、3≦e+f≦8の関係を満たす。また、gは1〜4の範囲の整数であり、hは0〜500の範囲の整数である。)
[17] 更に、(d)粉体又は着色剤を含有する[11]〜[16]のいずれか1項に記載の化粧料。
[18] 前記の(d)成分が、平均粒子径が1nm〜20μmの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体よりなる群より選ばれる1種又は2種類以上である[17]に記載の化粧料。
[19] 前記の(d)成分が、その一部または全部が撥水化処理された粉体もしくは着色剤である[17]または[18]に記載の化粧料。
[20] 更に、(e)水溶性高分子を含有する、[11]〜[19]のいずれか1項に記載の化粧料。
[21] 更に、(f)シリコーン樹脂を含有する、[11]〜[20]のいずれか1項に記載の化粧料。
[22] 更に、(g)シリコーンエラストマーを含有する、[11]〜[21]のいずれか1項に記載の化粧料。
[23] 更に、(h)紫外線防御成分を含有する、[11]〜[22]のいずれか1項に記載の化粧料。
[24] 化粧料が、スキンケア製品、毛髪用化粧料製品、制汗剤製品、メイクアップ製品、又は紫外線防御製品である、[11]〜[23]のいずれか1項記載の化粧料。
[25] 製品の形態が、液状、乳液状、クリーム状、固形状、ペースト状、ゲル状、粉末状、多層状、ムース状、スプレー状のいずれかである、[11]〜[24]のいずれか1項記載の化粧料。」により達成される。
「[26] (A)下記一般式(1’)で示される分子鎖両末端に珪素結合水素原子を有するオルガノポリシロキサンと、(B)下記一般式(2’)で表される分子鎖末端に1個の炭素−炭素二重結合を有するカルボシロキサンデンドロン構造を有する化合物{成分(A)に対して1/2モル等量以下となる量}を(C)ヒドロシリル化反応触媒の存在下において付加反応させた後、(D)分子鎖末端に1個のアルケニル基を有する親水性化合物{成分(A)に対して1/2モル等量以下となる量}をさらに付加反応させることを特徴とする、[1]に記載のオルガノポリシロキサン共重合体の製造方法。
一般式(1’):
(式中、R1は独立に炭素原子数1〜10のアルキル基またはアリール基であり、nは0〜10の範囲の数である。)
一般式(2’):
{式中、L´1はメチル基またはj=1のときの下記一般式(2’’)で示されるシリルアルキル基である。Z’は二価の有機基である。
(式中、R2は炭素原子数1〜6のアルキル基またはフェニル基であり、Zは二価の有機基である。jはLjで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がc’のとき1〜c’の整数であり、階層数c’は1〜10の整数であり、Lj+1はjがc’未満のときは該シリルアルキル基であり、j=c’のときはメチル基またはフェニル基である。ajは0〜3の範囲の数である。)}」により達成される。
上式中、R1は独立に炭素原子数1〜10のアルキル基またはアリール基である。L1はi=1のときの下記一般式(2)で示されるシリルアルキル基であり、nは0〜10の範囲の数であり、Qは親水性セグメントである。
一般式(2):
上式中、R2は炭素原子数1〜6のアルキル基またはフェニル基であり、Zは二価の有機基である。iはLiで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がcのとき1〜cの整数であり、階層数cは1〜10の整数であり、Li+1はiがc未満のときは該シリルアルキル基であり、i=cのときはメチル基またはフェニル基である。aiは0〜3の範囲の数である。
上式(3−1)で示される親水性単位はオキシアルキレン単位である。式中、rは1〜6の範囲の数であり、2〜4の範囲の数であることがより好ましい。上式(3−1)で示される親水性単位はQである親水性セグメントに1以上含有されることができる。また、(3−1)で示される親水性単位は、rが各々独立に2〜4であり、式(3−1)で示される親水性単位が2〜50個連結したポリオキシアルキレン単位として、Qである親水性セグメントに含有されていることが好ましい。
−(C2H4O)t1(C3H6O)t2− (3−1−1)
式中、t1およびt2は各々0以上の数であり、(t1+t2)は4〜50の範囲の数であり、好ましくは8〜30の範囲の数である。
−R3(−O−X1 m−R4)p (4−1)
(式中、R6は、各々独立に、置換基を有していてもよい、炭素数2〜22の直鎖状若しくは分岐鎖状のアルキレン基、アルケニレン基又は炭素数6〜22のアリーレン基である。)
−R3(−O−X2)p (4−2)
式中、2つの酸素原子には、各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。当該親水性単位は、さらに、構造式(3−5)〜(3−7)で表される基から選択される分岐単位に結合してもよく、親水性単位が多階層に分岐してなる樹状のポリエーテル構造、ポリグリセロール構造またはポリグリシジルエーテル構造を形成していても良い。
−R3(−O−X3)p (4−3)
式中、2つの酸素原子には、各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。当該親水性単位は、さらに、構造式(3−5)〜(3−7)で表される基から選択される分岐単位に結合してもよく、親水性単位が多階層に分岐してなる樹状のポリエーテル構造、ポリグリセロール構造またはポリグリシジルエーテル構造を形成していても良い。
−R3(−O−X4)p (4−4)
R3は前記同様の基であり、pは前記同様の数である。X4は下記構造式(4−4−1)で表される親水性単位である。
式中、2つの酸素原子には、各々独立に、上記一般式(3−1)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。当該親水性単位は、さらに、構造式(3−5)〜(3−7)で表される基から選択される分岐単位に結合してもよく、親水性単位が多階層に分岐してなる樹状のポリエーテル構造、ポリグリセロール構造またはポリグリシジルエーテル構造を形成していても良い。
{式中、L´1はメチル基またはj=1のときの下記一般式(2’’)で示されるシリルアルキル基である。Z’は二価の有機基である。
(式中、R2は炭素原子数1〜6のアルキル基またはフェニル基であり、Zは二価の有機基である。jはLjで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がc’のとき1〜c’の整数であり、階層数c’は1〜10の整数であり、Lj+1はjがc’未満のときは該シリルアルキル基であり、j=c’のときはメチル基またはフェニル基である。ajは0〜3の範囲の数である。)}
1.目的の粉体を、処理剤を配合した有機溶剤から選択される媒体中に分散して表面処理する方法。
2.粉体と粉体処理剤を混合したのち、ボールミル、ジェットミルなどの粉砕器を用いて表面処理する方法。
3.処理剤を溶剤に配合し、粉体を分散させて表面に吸着させた後、乾燥して焼結させる処理方法。
1.前記の如くして得た粉体組成物を、エステル油やシリコーン油等の油剤中に添加して分散する方法。
2.上記の油剤中にオルガノポリシロキサン共重合体を溶解または分散し、これに粉体を添加してボールミル、ビーズミル、サンドミル等の分散機器で混合する方法。そして、得られた油中粉体分散物は、そのまま化粧料に配合することができる。
一般式(6):
一般式(7):
一般式(8):
R4−gSi(OSiMe3)g (8)
本発明に係る(A)オルガノポリシロキサン共重合体を配合した化粧料に粉体のシリコーンエラストマーを添加すると、油剤に分散した時に得られるようなコクのある感触を与え、肌の凹凸を目立たなくし、かつ油剤と異なり油っぽいテカテカした質感や肌の油光りを抑制して自然な印象を与えるという利点がある。
(1)「P1」: 下記構造式(PI)において、a=1,b=4であるAB型オルガノポリシロキサン共重合体
(2)「P2」: 下記構造式(PI)において、a=3,b=4であるAB型オルガノポリシロキサン共重合体
(3)「P3」: 下記構造式(PI)において、a=1,b=1であるAB型オルガノポリシロキサン共重合体
(4)「P4」: 下記構造式(PI)において、a=1,b=2であるAB型オルガノポリシロキサン共重合体
構造式(PI):
(6)「P6」: 下記構造式(PII)において、a=1,c=9.2であるAB型オルガノポリシロキサン共重合体
構造式(PII):
攪拌装置,温度計,還流管を取り付けた2リットル4つ口フラスコに、1,3−ジヒドロジシロキサン624gを加え、75℃まで加熱し、トリストリメチルシロキシビニルシラン300gと白金触媒464mgの混合物を3時間かけて滴下した。1時間エージングした後、ガスクロマトグラフィーによりトリストリメチルシロキシビニルシランの消失を確認した。余剰の1,3−ジヒドロジシロキサンを、減圧下で除き、続いてテトラグリセリンモノアリルエーテル412gとIPA412gの混合溶液を滴下した。6時間100℃でエージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、前記のオルガノポリシロキサン共重合体P1を得た。収量は600g(収率79%)であった。分子量810。生成物はNMRスペクトルを用いて同定確認した。生成物の屈折率は、1.451であり、性状は、淡黄色粘性液体であった。
攪拌装置,温度計,還流管を取り付けた1リットル4つ口フラスコに、1,3−ジヒドロジシロキサン300gを加え、75℃まで加熱し、トリストリメチルシロキシヘキセニルシラン169gと白金触媒235mgの混合物を2時間かけて滴下した。1時間エージングした後、ガスクロマトグラフィーによりトリストリメチルシロキシヘキセニルシランの消失を確認した。余剰の1,3−ジヒドロジシロキサンを、減圧下で除き、続いてテトラグリセリンモノアリルエーテル198gとIPA198gの混合溶液を滴下した。6時間100℃でエージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、前記のオルガノポリシロキサン共重合体P2を得た。収量は310g(収率80%)であった。分子量866。生成物はNMRスペクトルを用いて同定確認した。生成物の屈折率は、1.450であり、性状は、淡黄色粘性液体であった。
攪拌装置,温度計,還流管を取り付けた2リットル4つ口フラスコに、1,3−ジヒドロジシロキサン936gを加え、75℃まで加熱し、トリストリメチルシロキシビニルシラン450gと白金触媒174mgの混合物を4時間かけて滴下した。1時間エージングした後、ガスクロマトグラフィーによりトリストリメチルシロキシビニルシランの消失を確認した。余剰の1,3−ジヒドロジシロキサンを、減圧下で除き、続いてグリセリンモノアリルエーテル231gを滴下した。7時間100℃でエージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、前記のオルガノポリシロキサン共重合体P3を得た。収量は800g(収率97%)であった。分子量588。生成物はNMRスペクトルを用いて同定確認した。生成物の屈折率は1.431であり、性状は、淡黄色粘性液体であった。
攪拌装置,温度計,還流管を取り付けた2リットル4つ口フラスコに、1,3−ジヒドロジシロキサン658gを加え、75℃まで加熱し、トリストリメチルシロキシビニルシラン316gと白金触媒244mgの混合物を3時間かけて滴下した。1時間エージングした後、ガスクロマトグラフィーによりトリストリメチルシロキシビニルシランの消失を確認した。余剰の1,3−ジヒドロジシロキサンを、減圧下で除き、続いてジグリセリンモノアリルエーテル200gとIPA200gの溶液を滴下した。2時間100℃でエージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、前記のオルガノポリシロキサン共重合体P4を得た。収量は515g(収率79%)であった。分子量662。生成物はNMRスペクトルを用いて同定確認した。生成物の屈折率は1.439であり、性状は、淡黄色粘性液体であった。
攪拌装置,温度計,還流管を取り付けた2リットル4つ口フラスコに、1,3−ジヒドロジシロキサン936gを加え、75℃まで加熱し、トリストリメチルシロキシビニルシラン450gと白金触媒174mgの混合物を4時間かけて滴下した。1時間エージングした後、ガスクロマトグラフィーによりトリストリメチルシロキシビニルシランの消失を確認した。余剰の1,3−ジヒドロジシロキサンを、減圧下で除き、続いてアリルポリエーテル371gを滴下した。3時間100℃でエージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、前記のオルガノポリシロキサン共重合体P5を得た。収量は930g(収率99%)であった。分子量668。生成物はNMRスペクトルを用いて同定確認した。生成物の屈折率は1.433であり、性状は、淡黄色粘性液体であった。
攪拌装置,温度計,還流管を取り付けた1リットル4つ口フラスコに、1,3−ジヒドロジシロキサン558gを加え、75℃まで加熱し、トリストリメチルシロキシビニルシラン268gと白金触媒207mgの混合物を3時間かけて滴下した。1時間エージングした後、ガスクロマトグラフィーによりトリストリメチルシロキシビニルシランの消失を確認した。余剰の1,3−ジヒドロジシロキサンを、減圧下で除き、続いてアリルポリエーテル381gの溶液を滴下した。4時間100℃でエージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、前記のオルガノポリシロキサン共重合体P6を得た。収量は671g(収率88%)であった。分子量919。生成物はNMRスペクトルを用いて同定確認した。生成物の屈折率は1.443であり、性状は、淡黄色粘性液体であった。
攪拌装置,温度計,還流管を取り付けた1リットル4つ口フラスコに、テトラグリセリンモノアリルエーテル291gとIPA291gの混合溶液を加え、75℃まで加熱した。白金触媒296mgを加えた後、先に得られた化学式 300gを滴下した。8時間エージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、合成例1の化合物(オルガノポリシロキサン共重合体P1)を得た。収量は421g(収率79%)であった。生成物はNMRスペクトルを用いて同定確認した。
攪拌装置,温度計,還流管を取り付けた500ミリリットル4つ口フラスコに、グリセリンモノアリルエーテル109gを加え、75℃まで加熱した。白金触媒76mgを加えた後、先に得られた化学式 300gを滴下した。7時間エージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、合成例3の化合物(オルガノポリシロキサン共重合体P3)を得た。収量は349g(収率90%)であった。生成物はNMRスペクトルを用いて同定確認した。
攪拌装置,温度計,還流管を取り付けた1リットル4つ口フラスコに、ジグリセリンモノアリルエーテル200gとIPA200gの混合溶液を加え、100℃まで加熱した。白金触媒139mgを加えた後、先に得られた化学式 354gを滴下した。2時間エージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、合成例4の化合物(オルガノポリシロキサン共重合体P4)を得た。収量は515g(収率99%)であった。生成物はNMRスペクトルを用いて同定確認した。
攪拌装置,温度計,還流管を取り付けた500ミリリットル4つ口フラスコに、アリルポリエーテル174gを加え、80℃まで加熱した。白金触媒175mgを加えた後、先に得られた化学式 300gを滴下した。8時間エージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、合成例5の化合物(オルガノポリシロキサン共重合体P5)を得た。収量は407g(収率93%)であった。生成物はNMRスペクトルを用いて同定確認した。
攪拌装置,温度計,還流管を取り付けた1リットル4つ口フラスコに、アリルポリエーテル381gとIPA381gの混合溶液を加え、80℃まで加熱した。白金触媒170mgを加えた後、先に得られた化学式 300gを滴下した。8時間エージングした後、Si−H結合の消失をIRスペクトルで確認した。減圧下、揮発分を除くことによって、合成例6の化合物(オルガノポリシロキサン共重合体P6)を得た。収量は605g(収率99%)であった。生成物はNMRスペクトルを用いて同定確認した。
(1)SS2910:ポリエーテル変性シリコーン(商品名:SS2910、東レ・ダウコーニング社製)
(2)FZ2233:直鎖状ブロック共重合体(ABn)タイプのポリエーテル変性シリコーン(商品名FZ−2233、東レ・ダウコーニング社製)
各組成の油中水型乳化組成物を室温(25℃)および40℃において1ヶ月間静置し、静置前後の乳化状態の変化を、以下の基準により評価した。
◎: 変化なし,○: 僅かに分離,△: 凝集発生、低粘度化
×: 分離・凝集
<評価基準>
10名のパネラーが評価対象である各組成の油中水型乳化組成物を化粧料として使用した場合の使用感(感触および伸びのよさ)を評価した。各パネラーこどにアンケートに回答してもらう形式にて、感触、伸びの良さが優れていると判断した場合には5点を、劣っていると判断した場合には1点を、中間については、2,3,4点を記入してもらい、その平均点を以て使用感の評価結果とした。
以下の[分散体の調製1]〜[分散体の調製3]に示す組成及び製法でスラリー状の微粒子分散体を調製し、その分散特性を流動特性の見地からを評価した。結果を図1および図2に示す。また、各分散体の調製において用いた成分は、以下の通りである。
(1) 微粒子粉体:微粒子酸化チタン
商品名:MTY−100SAS(テイカ社製)
粒子径:15nm
(2) 比較サンプル1:ポリエーテル変性シリコーン
商品名:SS2910(東レ・ダウコーニング社製)
(3) 比較サンプル2:ポリグリセリン変性シリコーン
(4) 分散媒:デカメチルシクロペンタシロキサン
商品名:DC245(東レ・ダウコーニング社製)
微粒子粉体20g、合成例1のオルガノポリシロキサン共重合体(P1)5gおよびデカメチルシクロペンタシロキサン25gを混合し、ジルコニアビーズ(0.8mmΦ)200gを加え、ペイントシェイカーにて1時間混合してスラリー状の分散体(D1)を作成した。
[分散体D1の調製]において、合成例1のオルガノポリシロキサン共重合体(P1)の代わりに、比較サンプル1であるポリエーテル変性シリコーンを用いた他は同様にして、スラリー状の分散体(D2)を作成した。
[分散体D1の調製]において、合成例1のオルガノポリシロキサン共重合体(P1)の代わりに、比較サンプル2であるポリグリセリン変性シリコーンを用いた他は同様にして、スラリー状の分散体(D3)を作成した。
微粒子粉体20g、合成例1のオルガノポリシロキサン共重合体(P1)5g、デカメチルシクロペンタシロキサン20gおよびトクオクタノイン5gを混合し、ジルコニアビーズ(0.8mmΦ)200gを加え、ペイントシェイカーにて1時間混合してスラリー状の分散体(D4)を作成した。
[分散体D4の調製]において、合成例1のオルガノポリシロキサン共重合体(P1)の代わりに、比較サンプル1であるポリエーテル変性シリコーンを用いた他は同様にして、スラリー状の分散体(D5)を作成した。
[分散体D4の調製]において、合成例1のオルガノポリシロキサン共重合体(P1)の代わりに、比較サンプル2であるポリグリセリン変性シリコーンを用いた他は同様にして、スラリー状の分散体(D6)を作成した。
(評価方法)
評価装置: TAインスツルメンツ社製 コーンプレート型粘度計 AR1000−N
測定条件: 40mml° スチール製ジオメトリー、せん断速度 0.01〜1000s−1、25℃
(結果)
分散媒にデカメチルシクロペンタシロキサンを用いたスラリー状の分散体(D1)〜(D3)の評価結果を図1に示す。
分散媒にデカメチルしクロペンタシロキサンおよびトリオクタノインを4:1の比で混合した溶液を用いたスラリー状の分散体(D4)〜(D6)の評価結果を図2に示す。
処方例
1.合成例1 1部
2.ジプロピレングリコール 1部
3.ジメチコン(6cs) 0.8部
4.フェニルトリメチコン(注1) 0.8部
5.PEG−12ジメチコン(注2) 1.4部
6.エタノール 20.3部
7.トリラウレス−4リン酸 0.15部
8.PEG−6コカミド 0.3部
9.PEG−3コカミド 0.2部
10.精製水 44.9部
11.カルノシン 0.1部
12.クエン酸 0.05部
13.ポリオキシプロピレンメチルグルコシド 0.4部
14.カーボマー(2%水溶液) 18部
15.水酸化ナトリウム(1%水溶液) 10.5部
注1:東レ・ダウコーニング社製 SH556を用いた。
注2:東レ・ダウコーニング社製 SH3775Mを用いた。
手順
1.成分1−9を混合する(A層)。
2.成分10−11を混合し、成分14,15を添加する(B層)。
3.B層にA層を添加し、乳化する。
効果
得られる化粧水は、安定な乳化状態を有しており、べたつきが少なく、感触に優れたものである。
1.合成例1 1部
2.ジプロピレングリコール 1部
3.ジメチコン(6cs) 0.8部
4.フェニルトリメチコン 0.8部
5.PEG−12ジメチコン(注1) 1.4部
6.エタノール 20.3部
7.ジメチコン(50cs) 10部
8.精製水 46部
9.カーボマー 0.45部
10.水酸化ナトリウム(1%) 10.5部
11.ポリオキシプロピレンメチルグルコシド 0.4部
12.1,3−ブチレングリコール 7部
13.エタノール 5部
14.グリセリン 8部
15.防腐剤 0.05部
(注1)東レ・ダウコーニング社製SH3775Mを用いた。
手順
1.成分1−7を混合する。(混合物1)
2.成分8−10を混合する。(混合物2)
3.成分11−15を混合する。(混合物3)
4.混合物2に混合物1を加え、乳化する。
5.さらに、混合物3を加え、攪拌する。
効果
得られるクレンジングジェルは、シリコーンを高配合でき、べたつきが少なく感触に優れる。
1.合成例2 1部
2.ジプロピレングリコール 1部
3.トリ(POE)ラウレスリン酸ナトリウム 0.05部
4.メトキシ桂皮酸エチルヘキシル 8.5部
5.t−ブチルメトキシベンゾイルメタン 1.5部
6.フェニルトリメチコン 3.4部
7.PEG12−ジメチコン(注1) 0.7部
8.ジメチコン(6cs) 1.4部
9.エタノール 7.35部
10.ビス(ヒドロキシエトキシ)ジメチコン(注2) 1部
11.カルボマー(2%溶液) 22.5部
12.精製水 残余
13.水酸化ナトリウム(1%aq) 10.5部
14.エタノール 2部
15.1,3−ブチレングリコール 5部
16.グリセリン 5部
17.防腐剤 0.05部
注1:東レ・ダウコーニング社製SS2804を用いた。
注2:東レ・ダウコーニング社製DC5562を用いた。
手順
1.成分1−10を混合する。(混合物1)
2.成分11−16を混合する。(混合物2)
3.混合物2に混合物1を加え、乳化する。
4.混合物3を加え、攪拌する。
効果
得られたサンスクリーンクリームは、安定な乳化状態を有しており、皮膚に塗布した場合には撥水性を有する。
1.メトキシ桂皮酸オクチル 10部
2.酸化チタンスラリー(注1) 1部
3.酸化亜鉛スラリー(注2) 32部
4.シクロペンタシロキサン 20.2部
5.ジメチコンクロスポリマー 3部
6.トリメチルシロキシケイ酸 3.3部
7.防腐剤 0.1部
8.エタノール 5部
9.1,3−ブチレングリコール 3部
10.精製水 残余
手順
1.微粒子酸化チタン(テイカ製、MTY−100SAS)40部、デカメチルペンタシクロシロキサン50部、合成例3 10部の組成で混合し、ジルコニアビーズ(0.8mmΦ)を添加しペイントシェーカーを用い酸化チタンスラリーを作成する。
2.微粒子酸化亜鉛(テイカ製、MZY−505S)40部、デカメチルペンタシクロシロキサン 50部、合成例3 10部の組成で混合し、ジルコニアビーズ(0.8mmΦ)を添加しペイントシェーカーで酸化亜鉛スラリーを作成する。
3.成分1−8を混合する。
4.手順3の混合物に、成分9,10の混合物を添加し、乳化する。
効果
得られたサンスクリーンは、肌上に塗布したときに、べたつきが低減されており優れた使用感を有し、持続性のある紫外線保護効果を与える。
1.メトキシ桂皮酸オクチル 7.5部
2.シクロペンタシロキサン 8部
3.ジメチコン(6cs) 2部
4.シクロペンタシロキサン/(アクリレーツ/メタクリル酸ポリトリメチルシロ
キシ)コポリマー(注1) 1部
5.ジメチコンクロスポリマー(注2) 2部
6.ポリシリコーン13(注3) 1部
7.合成例1 1部
8.酸化チタンスラリー(30%)(注4) 2部
9.酸化亜鉛スラリー(50%)(注5) 10部
10.塩化ナトリウム 1部
11.パンテノール 0.5部
12.精製水 残余
13.グリセリン 2部
14.防腐剤 0.05部
注1:東レ・ダウコーニング社製FA4001CM Silicone Acrylateを使用した。
注2:東レ・ダウコーニング社製DC9041を使用した。
注3:直鎖状ブロック共重合体(ABn)タイプのポリエーテル変性シリコーン:東レ・ダウコーニング社製FZ−2233を使用した。
注4:分散剤に合成例6を用いた以外は、処方4の酸化チタンスラリーと同様の組成でスラリーを作成した。
注5:分散剤に合成例6を用いた以外は、処方4の酸化亜鉛スラリーと同様の組成でスラリーを作成した。
手順
1.成分1−9を混合する。(混合物1)
2.成分10−14を混合する。(混合物2)
3.混合物1に混合物2をディスパーで攪拌しながら添加する。
効果
得られたサンスクリーンクリームは、粉体が効率的に分散されているため、肌上に塗布したときに、べたつきが低減されており優れた使用感を有し、持続性のある紫外線保護効果を与える。
1.パルミチン酸デキストリン 2.1部
2.トリ(カプリル・カプリン酸)グリセリル 5部
3.PEG/PPG−18/18ジメチコン(注1) 10部
4.合成例10 1.9部
5.ジメチコン(2cs) 10部
6.シクロペンタシクロシロキサン 10部
7.シリコーン処理赤、黄、黒酸化鉄 3.5部
8.マイカ 3.5部
9.シリコーン処理酸化チタン 4部
10.精製水 残余
11.塩化ナトリウム 1部
注1:東レ・ダウコーニング社製BY11−030を使用した。
手順
成分1〜6を混合しておき、そこにあらかじめ粉砕しておいた成分6−9を添加・分散した後、溶解混合しておいた成分10−11を徐添しながら乳化し、液状ファンデーションを得る。
効果
得られたファンデーションは、乳化安定性に優れ、化粧持ちに優れる。
1.ジメチコン/ビニルジメチコンクロスポリマー・シリカ(注1) 4部
2.合成例5 3部
3.PEG/PPG−18/18ジメチコン 7部
4.シクロペンタシロキサン 16部
5.PPG−ミリスチルエーテル 0.5部
6.精製水 残余
7.グリセリン 5部
8.塩化ナトリウム 2部
9.防腐剤 0.5部
注1:東レ・ダウコーニング社製9701 Cosmetic Powderを使用した。
手順
1.成分1−5を混合する。(混合物1)
2.成分6−9を混合する。(混合物2)
3.混合物1に混合物2を添加して、乳化する。
効果
得られた化粧料は、乳化安定性に優れ、べたつきが少なく、優れた使用感を有する。
1.セレシンワックス 10部
2.パラフィンワックス 8部
3.キャンデリラワックス 2部
4.流動パラフィン 21.8部
5.液状ラノリン 10部
6.イソノナン酸イソデシル 25部
7.トリ(カプリル/カプリン)酸グリセリル 5部
8.合成例9 9部
9.イソドデカン/(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポ
リマー(注1) 1部
10.酸化チタン 2部
11.赤色201号 2部
12.赤色202号 1部
13.黄色号アルミニウムレーキ 3部
14.抗酸化剤 0.1部
15.香料 0.1部
注1:東レ・ダウコーニング社製FA4002IDSilicone Acrylateを使用した。
手順
全ての成分を加熱混合して、型に流し込む。
効果
得られた口紅は、油性原料のなじみがよく、貯蔵安定性に優れ、塗布した際の発色、艶に優れる。
(成分) (Wt%)
1.ジメチルポリシロキサン(2cs) 13.0
2.ジメチルポリシロキサン(6cs) 12.0
3.合成例11 2.0
4.PEG(10)ラウリルエ−テル 0.5
5.オクチルシラン処理酸化チタン 6.2
6.オクチルシラン処理セリサイト 4.0
7.オクチルシラン処理マイカ 6.0
8.塩化ナトリウム 2.0
9.プロピレングリコール 8.0
10. 防腐剤 適量
11. 香料 適量
12. 精製水 残余
手順
A : 成分1〜4を混合し、成分5〜7を添加して均一に分散する。
B : 成分8〜12を均一溶解する。
C : 攪拌下、AにBを徐添して乳化し、アイシャドウを得る。
効果
得られたアイシャドウは、使用時になめらかに伸びて、発色に優れる。
(成分) (Wt%)
1.イソヘキサデカン 34.0
2.ジメチコン(6cs) 1.5
3.トリメチルシロキシケイ酸(注1) 31.0
4.デキストリン脂肪酸エステル 15.0
5.合成例8の組成物 3.0
6.有機変性ベントナイト 1.5
7.疎水化無水ケイ酸 2.0
8.ナイロン繊維(平均長さ2μm) 2.0
9.カーボンブラック 10.0
手順
成分1〜9を混合して均一化し、容器に充填してマスカラを得る。
効果
得られたマスカラは、使用時に深みのある外観を有し、つやに優れる。また、睫への密着性が良好であり、持続性に優れる。
Claims (12)
- 下記一般式(1)で示されるオルガノポリシロキサン共重合体。
一般式(1):
一般式(2):
Qは二価以上の連結基を介してケイ素原子に結合し、かつ下記構造式(3−2)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位を含有してなる親水性セグメントである。
- 一般式(1)において、Qが下記一般式(4−1)〜(4−4)で示される親水性セグメントである、請求項1〜3のいずれか1項に記載のオルガノポリシロキサン共重合体。
一般式(4−1):
−R3(−O−X1 m−R4)p (4−1)
(式中、R3は(p+1)価の有機基であり、pは1以上の数である。X1は各々独立に、上記一般式(3−2)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位であり、mは1〜100の範囲の数である。R4は水素原子、炭素原子数1〜20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。)
一般式(4−2):
−R3(−O−X2)p (4−2)
{式中、R3は前記同様の基であり、pは前記同様の数である。X2は下記構造式(4−2−1)で表される親水性単位である。
一般式(4−3):
−R3(−O−X3)p (4−3)
{式中、R3は前記同様の基であり、pは前記同様の数である。X3は下記構造式(4−3−1)で表される親水性単位である。
一般式(4−4):
−R3(−O−X4)p (4−4)
{式中、R3は前記同様の基であり、pは前記同様の数である。X4は下記構造式(4−4−1)で表される親水性単位である。
- 下記構造式(1−1)〜(1−4)のいずれかで示されることを特徴とする、請求項1〜4のいずれか1項に記載のオルガノポリシロキサン共重合体。
構造式(1−1):
X1は各々独立に、上記一般式(3−2)〜(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位である。
R’3は下記一般式(5−1),(5−1−2),(5−1−3)または(5−2)で示される2価の有機基から選択される基である。
R4は水素原子、炭素原子数1〜20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。
R5は下記一般式(5−1)〜(5−7)で示される2価の有機基から選ばれる基である。
- n=0であることを特徴とする、請求項1〜5のいずれか1項に記載のオルガノポリシロキサン共重合体。
- 請求項1〜6のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する界面活性剤。
- 請求項1〜6のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する粉体処理剤。
- 請求項1〜6のいずれか1項に記載のオルガノポリシロキサン共重合体を含有する外用剤組成物。
- 化粧料または医薬である請求項9に記載の外用剤組成物。
- 以下の構成成分を含有する、請求項10に記載の外用剤組成物。
(a)請求項1〜6のいずれか1項に記載のオルガノポリシロキサン共重合体 0.1〜99.9重量%
(b)シリコーンオイル、非極性有機化合物または低極性有機化合物 99.9〜0.1重量%
- スキンケア製品、毛髪用化粧料製品、制汗剤製品、メイクアップ製品、又は紫外線防御製品である、請求項10または11に記載の外用剤組成物。
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WO2011049248A1 (ja) | 2009-10-23 | 2011-04-28 | 東レ・ダウコーニング株式会社 | 新規な共変性オルガノポリシロキサン |
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US9585832B2 (en) | 2011-05-30 | 2017-03-07 | Dow Corning Toray Co., Ltd. | Organopolysiloxane elastomer modified with mono-/diglycerin derivative, and use therefor |
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US9133309B2 (en) | 2015-09-15 |
KR101768154B1 (ko) | 2017-08-16 |
EP2492300A1 (en) | 2012-08-29 |
WO2011049246A1 (ja) | 2011-04-28 |
EP2492300A4 (en) | 2013-10-09 |
US20120269747A1 (en) | 2012-10-25 |
KR20120094933A (ko) | 2012-08-27 |
JPWO2011049246A1 (ja) | 2013-03-14 |
CN102666663A (zh) | 2012-09-12 |
EP2492300B1 (en) | 2018-10-03 |
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